WO2023037797A1 - 複合微粒子、太陽電池、光電変換素子用部材、および光電変換素子 - Google Patents

複合微粒子、太陽電池、光電変換素子用部材、および光電変換素子 Download PDF

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WO2023037797A1
WO2023037797A1 PCT/JP2022/029739 JP2022029739W WO2023037797A1 WO 2023037797 A1 WO2023037797 A1 WO 2023037797A1 JP 2022029739 W JP2022029739 W JP 2022029739W WO 2023037797 A1 WO2023037797 A1 WO 2023037797A1
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layer
coating layer
metal
fine particles
photoelectric conversion
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French (fr)
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あゆみ 二瓶
力 宮坂
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国立研究開発法人科学技術振興機構
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Priority to KR1020247006659A priority Critical patent/KR20240039019A/ko
Priority to CN202280059197.9A priority patent/CN117898039A/zh
Priority to JP2023546833A priority patent/JPWO2023037797A1/ja
Publication of WO2023037797A1 publication Critical patent/WO2023037797A1/ja

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    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
    • H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
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    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to composite fine particles, solar cells, photoelectric conversion element members, and photoelectric conversion elements. This application claims priority based on Japanese Patent Application No. 2021-147994 filed in Japan on September 10, 2021, the content of which is incorporated herein.
  • Photoelectric conversion elements such as solar cells and photodiodes are widely used in various fields.
  • conventional photoelectric conversion elements have a problem that they have a lower detection sensitivity to light in the near-infrared region than to light in the visible light region. If the detection sensitivity for light in the near-infrared region can be increased in the same way as for visible light, the photoelectric conversion efficiency can be improved, for example, in a solar cell. Therefore, there is a demand for a photoelectric conversion element that has high detection sensitivity for light in the near-infrared region as well as for visible light.
  • a core/shell type Ln complex nanoparticle is disclosed, which is characterized by coordinating a ligand having a moiety represented by:
  • Patent Document 1 for light in the near-infrared region.
  • the present invention is an invention made in view of the above circumstances, and provides composite fine particles, a solar cell, a member for a photoelectric conversion element, and a photoelectric conversion element having excellent detection sensitivity to light in the near-infrared or infrared region. intended to provide
  • the composite fine particles according to one aspect of the present invention include inorganic fine particles having a light wavelength conversion capability and a continuous or discontinuous first coating formed on the whole or part of the surface of the inorganic fine particles. a second coating layer formed on the first coating layer; and a third coating layer formed on the second coating layer, wherein the second coating layer is near-infrared or infrared It is an organic compound having light absorption in the outer region and contains a multidentate organic ligand having at least two coordination sites, and the first coating layer is coordinated with the multidentate organic ligand.
  • the inorganic fine particles may contain a metal that is a rare earth element capable of emitting excitation light in the visible or ultraviolet region.
  • the polydentate organic ligand absorbs energy generated by light absorption in the near-infrared or infrared region to the transition metal contained in the first coating layer.
  • the metal which is a rare earth element capable of emitting excitation light in the visible or ultraviolet region, contained in the inorganic fine particles, wavelength-converted light emission by the inorganic fine particles may be enabled.
  • the transition metal contained in the first coating layer may be a lanthanide metal.
  • the third coating layer may be an inorganic compound layer made of an inorganic perovskite-type substance.
  • the first coating layer comprises a metal layer or an inorganic compound layer containing the coordination metal, and the coordination metal. It may be a multilayer including a metal layer or an inorganic compound layer containing the same or different transition metals.
  • the fine composite particles according to any one of (1) to (6) above have a substantially spherical or polygonal shape and an average particle diameter of 1 nm or more and 1 ⁇ m or less. good too.
  • a solar cell according to an aspect of the present invention includes a photoelectric conversion layer containing the composite fine particles according to any one of (1) to (7) above and an inorganic perovskite-type substance.
  • the solar cell described in (8) above may further include an electron transport layer made of titanium (IV) oxide.
  • a photoelectric conversion element member comprises a layer containing the composite fine particles described in any one of (1) to (7) above and an organic semiconductor or an inorganic semiconductor as main components.
  • a layer consisting of aggregates or thin films with the following is laminated.
  • a photoelectric conversion element includes the photoelectric conversion element member according to (10) above, a hole transport layer, an electron transport layer, wherein the photoelectric conversion element member is disposed between the hole transport layer and the electron transport layer.
  • FIG. 1 is a cross-sectional view of composite microparticles according to one embodiment of the present invention.
  • FIG. FIG. 5 is a cross-sectional view of composite fine particles according to a modification of the present invention.
  • FIG. 2 is a cross-sectional view of a photoelectric conversion element provided with the composite fine particles of FIG. 1; 4 shows the energy band structure of each layer during operation of the photoelectric conversion element of FIG. 3 ;
  • FIG. 2 is a cross-sectional view of a modification of the photoelectric conversion element provided with the fine composite particles of FIG. 1;
  • FIG. 2 is a cross-sectional view of a modification of the photoelectric conversion element provided with the fine composite particles of FIG. 1; 7 shows the energy band structure of each layer during operation of the photoelectric conversion device of FIG.
  • FIG. 4 is a cross-sectional view of an object to be processed in the manufacturing process of the photoelectric conversion element of FIG. 3;
  • FIG. 1 is an SEM image of a first intermediate particle, a second intermediate particle, a third intermediate particle, and an AFM image of a fourth intermediate particle;
  • 4 is an SEM image of composite fine particles A and composite fine particles B.
  • FIG. 4 is a graph showing changes in absorptance of excitation light irradiated to composite fine particles A and nano fine particles A (comparative fine particles having no second coating layer).
  • 4 is a graph showing an emission spectrum of Composite Fine Particles A.
  • FIG. 4 is a graph showing an emission spectrum of composite microparticles B.
  • FIG. 4 is a graph showing current-voltage characteristics of the photoelectric conversion element of Example 1.
  • FIG. 1 is a cross-sectional view schematically showing the configuration of composite fine particles 10 of the present invention.
  • the composite fine particles 10 are composed of an inorganic fine particle 1 having a light wavelength conversion capability, a continuous or discontinuous first coating layer 2 formed on the whole or a part of the surface of the inorganic fine particle 1, and a first coating layer 2 and a third coating layer 4 formed on the second coating layer 3 .
  • the average particle size of the composite fine particles 10 is, for example, 1 nm or more and 1 ⁇ m or less.
  • a preferable average particle size of the fine composite particles 10 is 1 nm or more and 100 nm or less. More preferably, the average particle size of the fine composite particles 10 is 10 nm or more and 100 nm or less. More preferably, the average particle size of the fine composite particles 10 is 10 nm or more and 50 nm or less.
  • the particle size can be measured from an observed image of the fine composite particles 10 obtained by observation with a scanning electron microscope, for example. In the observed image, the average particle size of the composite fine particles 10 may be the average value of the particle sizes of 10 arbitrarily selected composite fine particles 10 .
  • the shape of the composite fine particles 10 is not particularly limited, and may be, for example, substantially spherical, polygonal parallelepiped, scale-like, or needle-like.
  • the shape of the fine composite particles 10 is preferably approximately spherical or polygonal.
  • the inorganic fine particles 1 have the ability to convert the wavelength of light.
  • the wavelength conversion ability of light means the ability to convert the wavelength of incident light and emit light having a wavelength different from that of the incident light.
  • incident near-infrared light or light in the infrared region is converted in wavelength and emitted as visible light will be described as an example.
  • Main materials of the inorganic fine particles 1 include, for example, erbium (Er), thulium (Tm), ytterbium (Yb), neodymium (Nd), holmium (Ho), praseodymium (Pr), gadolinium (Gd), europium (Eu ), terbium (Tb), samarium (Sm), cerium (Ce), promethium (Pm), dysprosium (Dy), etc., which are rare earth elements capable of emitting excitation light in the visible or ultraviolet region, or compounds thereof Among them, those containing at least one are exemplified. Note that light in the visible or ultraviolet region means light with a wavelength of less than 700 nm.
  • the inorganic fine particles 1 include inorganic fine particles such as NaErF4 , Tm2O3 , TmCl3 , TmF3 , Er2O3 , ErCl3 , ErF3 , Ho2O3 , HoCl3 , and HoF3.
  • the inorganic fine particles 1 may be fine particles doped with a sensitizer (eg, Yb 3+ ) and a luminescent material (eg, Er 3+ , Ho 3+ , Tm 3+ ) as guests.
  • a sensitizer eg, Yb 3+
  • a luminescent material eg, Er 3+ , Ho 3+ , Tm 3+
  • Such fine particles include Yb, Er-doped Gd 2 O 2 S (Gd 2 O 2 S: Er, Yb), Yb 3+ , Er 3+ doped NaYF 4 (NaYF 4 : Er, Yb), Tm, Yb-doped NaYF 4 (NaYF 4 : Tm, Yb) and other inorganic fine particles.
  • the average particle size of the inorganic fine particles 1 is, for example, 1 nm to 1 ⁇ m.
  • a preferable average particle size of the inorganic fine particles 1 is 1 nm to 100 nm.
  • a more preferable average particle size of the inorganic fine particles 1 is 10 nm to 100 nm.
  • a more preferable average particle diameter of the inorganic fine particles 1 is 10 nm to 50 nm.
  • the shape of the inorganic fine particles 1 is not particularly limited, and is, for example, substantially spherical, polygonal parallelepiped, scale-like, or needle-like.
  • the shape of the inorganic fine particles 1 is preferably approximately spherical or polygonal.
  • the first coating layer 2 is a continuous or discontinuous layer formed on all or part of the surface of the inorganic fine particles 1 .
  • An example of the continuous first coating layer 2 is the case where the first coating layer 2 is laminated on the entire surface of the inorganic fine particles 1 .
  • An example of the discontinuous first coating layer 2 is an example in which the component of the inorganic fine particles 1 and the component of the first coating layer 2 are partially mixed (mixed). In the case of the discontinuous first coating layer 2 , there is a mixed region where there is no clear interface between the inorganic fine particles 1 and the first coating layer 2 .
  • the first coating layer 2 is a metal layer or an inorganic It is a compound layer.
  • the coordinating metal refers to a metal capable of coordinating with a polydentate organic ligand.
  • the coordinating metal is not particularly limited as long as it can form a coordinate bond with the polydentate organic ligand of the second coating layer 3 .
  • Examples of coordinating metals include transition metals.
  • the coordinating metal is more preferably a metal that is a rare earth element.
  • Lanthanide metals (Ln) such as Ce, Pr, Nd, Sm, Dy, Ho, Er, Tm, and Yb are more preferable as coordinating metals.
  • Coordination bonds are formed between the polydentate organic ligands of the second coating layer 3 and the first coating layer 2 because the first coating layer 2 contains the coordinating metal. Thereby, the energy transfer from the polydentate organic ligands in the second coating layer 3 can be efficiently promoted.
  • the first coating layer 2 contains a transition metal that is the same as or different from the coordination metal. Energy generated by light absorption in the second coating layer 3 is transferred to the inorganic fine particles 1 via the transition metal in the first coating layer 2 .
  • the transition metal of the first coating layer 2 is a metal that mediates energy transfer (energy mediating metal).
  • the energy mediating metal of the first coating layer 2 is preferably a metal that is a rare earth element. More preferably, the energy mediating metal of the first coating layer 2 is a lanthanide metal (Ln) such as Ce, Pr, Nd, Sm, Dy, Ho, Er, Tm, Yb.
  • the first coating layer 2 is a metal layer or inorganic compound layer containing a coordination metal and a transition metal (energy mediating metal).
  • the first coating layer 2 is an inorganic compound layer, for example, NaYbF 4 , NaNdF 4 , Yb(NO 3 ) 3 , Yb(CH 3 COO) 3 , Yb(CF 3 SO 3 ) 3 , Yb 2 (SO 4 ) 3 , Yb2 ( CO3 ) 3 , YbCl3 , YbBr3 , YbI3 and Er2O3 .
  • the thickness of the first coating layer 2 is not particularly limited, it may be 5% or more of the particle diameter of the inorganic fine particles 1, and it is preferably substantially uniform over the surface of the inorganic fine particles 1.
  • the thickness of the first coating layer 2 is, for example, 1 to 10 nm. More preferably, the thickness of the first covering layer 2 is 1-5 nm.
  • the coverage of the first coating layer 2 with respect to the surface of the inorganic fine particles 1 is preferably 50% or more. It is more preferable that the coverage of the first coating layer 2 of the inorganic fine particles 1 is 100%.
  • the second coating layer 3 is an organic compound having light absorption in the near-infrared or infrared region and contains a polydentate organic ligand having at least two coordination sites.
  • the near-infrared or infrared region refers to a wavelength range of 700 nm to 3000 nm, for example.
  • the polydentate organic ligand of the second coating layer 3 is an organic compound having a high absorption coefficient in the near-infrared or infrared region.
  • the multidentate organic ligand of the second coating layer 3 forms a coordinate bond with the first coating layer 2, so that the energy absorbed by the multidentate organic ligand is efficiently transferred through the energy mediating metal of the inorganic fine particles 1.
  • the inorganic fine particles 1 can be moved.
  • energy to the rare earth element contained in the inorganic fine particles 1 and capable of emitting excitation light in the visible or ultraviolet region it is possible to emit light having a wavelength different from that of the incident light. That is, the energy generated by the multidentate organic ligand absorbed by light in the near-infrared or infrared region is transferred to the inorganic fine particles 1 via the transition metal (energy-mediating metal) contained in the first coating layer 2.
  • the composite fine particles 10 can emit wavelength-converted light.
  • the polydentate organic ligand is not particularly limited as long as it has light absorption in the near-infrared or infrared region and has two or more coordination sites. Specific examples include a bidentate ligand having two coordination sites, a tetradentate ligand having four coordination sites, a hexadentate ligand having six coordination sites, and the like.
  • Typical multidentate organic ligands include, for example, the ligand compounds such as indocyanine dyes, quinone (quinoid) dyes, squalium dyes, cyanine dyes, phthalocyanine dyes, porphyrin dyes, Examples include azo compounds, coumarin dyes, indoline dyes, eosin, fluorescein, rhodamine, merocyanine, coumarin, indoline, and the like.
  • Examples of preferred multidentate organic ligands include indocyanine dyes represented by the following formula (1) and derivatives thereof, indigo dyes represented by the following formula (2) and derivatives thereof (where R For example, a sulfonic acid group and the like can be mentioned.), a squalium-based dye represented by the following formula (3) and a derivative thereof (here, R in the formula is, for example, an alkyl group, an adjacent aromatic an alkyl group forming a ring together with atoms on the ring, etc.).
  • the indocyanine dyes and derivatives thereof are compounds having a hexatriene basic skeleton, and representative compounds include indocyanine green (ICG).
  • the indigo dye and its derivatives are compounds having a bi(2,3-dihydroxy-3-oxoindolylidene) basic skeleton, and are typical compounds. Examples thereof include indigo carmine, etc.
  • the squarylium dye and its derivatives have a squarylic acid skeleton in the central part of the molecule, and two carbon atoms located on the diagonal line thereof are composed of aromatic compounds.
  • the thickness of the second coating layer 3 is not particularly limited as long as it can absorb incident light.
  • the thickness of the second coating layer 3 is, for example, a monomolecular film or more. Preferably, it is substantially a monomolecular film.
  • a third coating layer 4 is provided on the second coating layer 3 .
  • the third coating layer 4 is a metal layer or inorganic compound layer containing a coordinating metal capable of forming a coordinate bond with the polydentate organic ligand of the second coating layer 3 . Since the third coating layer 4 contains a coordinating metal, coordination bonds are formed with the polydentate organic ligands of the second coating layer 3 . Similarly, coordinate bonds are formed between the first covering layer 2 and the polydentate organic ligands of the second covering layer 3 . As a result, the polydentate organic ligands of the second coating layer 3 are firmly bound between the first coating layer 2 and the second coating layer 3 .
  • the polydentate organic ligands are strongly restrained, so that the thermal vibration of the polydentate organic ligands is suppressed. Thereby, the conversion efficiency of the composite microparticles 10 can be improved.
  • the coordinating metal of the third coating layer 4 is not particularly limited as long as it can form a coordinate bond with the polydentate organic ligand of the second coating layer 3 .
  • Examples of coordinating metals include transition metals.
  • the coordinating metal is more preferably a metal that is a rare earth element. Lanthanide metals (Ln) such as Ce, Pr, Nd, Sm, Dy, Ho, Er, Tm, and Yb are more preferable as coordinating metals.
  • the third coating layer 4 is preferably an inorganic compound layer made of an inorganic perovskite-type substance.
  • an inorganic perovskite-type substance By using an inorganic perovskite-type substance, the affinity with the photoelectric conversion layer is improved, and the photoelectric conversion efficiency is improved.
  • Yb-doped NaYF 4 (NaYF 4 : Er, Yb)
  • CsPbBr 3 or CsPbI 3 because the photoelectric conversion efficiency is improved.
  • Tm Yb-doped NaYF 4 (NaYF 4 :Tm, Yb)
  • CsPbCl 3 because the photoelectric conversion efficiency is improved.
  • the thickness of the third coating layer 4 is not particularly limited, it may be 5% or more of the particle size of the inorganic fine particles 1, and is preferably substantially uniform over the surface of the second coating layer 3.
  • the thickness of the third coating layer 4 is, for example, 1-10 nm. More preferably, the thickness of the third covering layer 4 is 1-5 nm.
  • the coverage of the third coating layer 4 with respect to the surface of the second coating layer 3 is preferably 50% or more. More preferably, the coverage of the third coating layer 4 with respect to the surface of the second coating layer 3 is 90% or more.
  • the coverage of the second coating layer 3 of the inorganic fine particles 1 may be 100%.
  • the composite fine particle 10A includes an inorganic fine particle 1 having a light wavelength conversion capability, a continuous or discontinuous first coating layer 2A formed on the whole or a part of the surface of the inorganic fine particle 1, and a first coating layer A second coating layer 3 formed on 2A and a third coating layer 4 formed on the second coating layer 3 are provided.
  • the first coating layer 2A is a continuous or discontinuous layer formed on all or part of the surface of the inorganic fine particles 1 .
  • the first coating layer 2A comprises a coordinating metal-containing layer 5A containing a coordinating metal and an energy mediating metal-containing layer 5B containing a transition metal that is the same as or different from the coordinating metal of the coordinating metal-containing layer 5A. It is a multi-layer containing.
  • An energy-mediating metal-containing layer 5B is formed on the surface of the inorganic fine particles 1, and a coordination metal-containing layer 5A is formed on the energy-mediating metal-containing layer 5B.
  • the coordinating metal-containing layer 5A contains Nd as a coordinating metal
  • the energy mediating metal-containing layer 5B contains Yb as an energy mediating metal.
  • the energy transfer from Nd to the emitter metals Er and Tm is inefficient, but such a layer structure can make the energy transfer more efficient.
  • the coordinating metal-containing layer 5A is a metal layer or inorganic compound layer containing a coordinating metal capable of forming a coordinate bond with the polydentate organic ligands of the second coating layer 3 .
  • the coordinating metal contained in the coordinating metal-containing layer 5A is not particularly limited as long as it can form a coordinate bond with the multidentate organic ligand of the second coating layer 3 .
  • Examples of coordinating metals include transition metals.
  • the coordinating metal is more preferably a metal that is a rare earth element. Lanthanoid metals such as Ce, Pr, Nd, Sm, Dy, Ho, Er, Tm and Yb are more preferable as coordinating metals. Since the coordinating metal-containing layer 5A contains the coordinating metal, a coordinate bond is formed between the multidentate organic ligand of the second coating layer 3 and the coordinating metal-containing layer 5A.
  • Examples of the coordinating metal-containing layer 5A include NaYbF 4 , NaNdF 4 , Yb(NO 3 ) 3 , Yb(CH 3 COO) 3 , Yb(CF 3 SO 3 ) 3 , Yb 2 (SO 4 ) 3 , Yb 2 (CO 3 ) 3 , YbCl 3 , YbBr 3 , YbI 3 and Er 2 O 3 and the like.
  • the energy mediating metal-containing layer 5B is a metal layer or inorganic compound layer containing a transition metal that is the same as or different from the coordinating metal of the coordinating metal-containing layer 5A.
  • the energy mediating metal-containing layer 5B contains a transition metal that is the same as or different from the coordinating metal. Energy generated by light absorption in the second coating layer 3 is transferred to the inorganic fine particles 1 via the transition metal in the energy-mediating metal-containing layer 5B.
  • the transition metal of the energy mediating metal-containing layer 5B is a metal (energy mediating metal) that mediates energy transfer.
  • the transition metal of the energy mediating metal-containing layer 5B is preferably a metal that is a rare earth element. Lanthanide metals (Ln) such as Ce, Pr, Nd, Sm, Dy, Ho, Er, Tm and Yb are more preferred.
  • Examples of the energy mediating metal-containing layer 5B include NaYbF 4 , NaNdF 4 , Yb(NO 3 ) 3 , Yb(CH 3 COO) 3 , Yb(CF 3 SO 3 ) 3 , Yb 2 (SO 4 ) 3 , Yb 2 (CO 3 ) 3 , YbCl 3 , YbBr 3 , YbI 3 and Er 2 O 3 and the like.
  • the thickness of the first coating layer 2A is not particularly limited, it may be 5% or more of the particle diameter of the inorganic fine particles 1, and it is preferably substantially uniform over the surface of the inorganic fine particles 1.
  • the thickness of the first covering layer 2A is, for example, 1 to 10 nm. More preferably, the thickness of the first covering layer 2A is 1-5 nm.
  • the thickness of the coordinating metal-containing layer 5A and the thickness of the energy mediating metal-containing layer 5B can be appropriately set so as to be the thickness of the first coating layer 2A.
  • the coverage of the first coating layer 2A with respect to the surface of the inorganic fine particles 1 is preferably 50% or more. It is more preferable that the coverage of the first coating layer 2A of the inorganic fine particles 1 is 100%.
  • FIG. 3 is a cross-sectional view of a photoelectric conversion element 100 having composite fine particles 10. As shown in FIG.
  • the photoelectric conversion element 100 is a photoelectric conversion element suitable for solar cells.
  • the photoelectric conversion element 100 mainly includes a positive electrode layer (positive electrode member) 101, a negative electrode layer (negative electrode member) 102, and a photoelectric conversion layer 103 sandwiched therebetween.
  • the energy level of the conduction band is Ecb
  • the energy level of the conduction band between the negative electrode layer 102 and the photoelectric conversion layer 103 is between Ec2 and Ec3 .
  • E c2 ⁇ E cb ⁇ E c3 may be sandwiched.
  • constituent materials of the buffer layer 107 include europium oxide (Eu 2 O 3 ), titanium oxide, and tin oxide.
  • the structure of the buffer layer 107 include a structure in which one or more of the constituent materials are laminated on the surface of the photoelectric conversion layer 103 on the negative electrode layer 102 side.
  • the negative electrode layer 102 is made of a light-transmitting material such as antimony-doped tin oxide (ATO), indium tin oxide (ITO), zinc oxide, tin oxide, fluorine-doped tin oxide ( FTO) or the like is preferable.
  • ATO antimony-doped tin oxide
  • ITO indium tin oxide
  • FTO fluorine-doped tin oxide
  • the positive electrode layer 101 does not have to be transparent, and metal, conductive polymer, etc. can be used as the electrode material for the electrode.
  • electrode materials include metals such as gold (Au), silver (Ag), aluminum (Al), zinc (Zn), and alloys of two or more thereof, graphite, graphite intercalation compounds, polyaniline and Derivatives include polythiophene and its derivatives.
  • a material for the transparent positive electrode layer 101 includes ITO.
  • the photoelectric conversion layer 103 is mainly composed of a plurality of particles (hereinafter sometimes referred to as "inorganic semiconductor particles") 20 containing an inorganic semiconductor as a main component.
  • (Electron transport layer) 104 formed on the surface of the first layer 104, containing an inorganic perovskite-type substance as a main component, and further comprising an aggregate or a thin film (composite) containing the composite fine particles 10
  • a layer 105 and a third layer 106 composed of a plurality of particles containing an organic or inorganic semiconductor (including a metal complex) as a main component, aggregates thereof, or a thin film are preferably laminated.
  • Photoelectric conversion layer 103 contains composite fine particles 10 and an inorganic perovskite-type substance.
  • containing an inorganic semiconductor as a main component means that the inorganic semiconductor particles 20 contain an amount capable of exhibiting the function of the present invention. It means that the semiconductor content is more than 50% by volume with respect to the total volume of the first layer 104 .
  • the inorganic perovskite-type material is more than 90% by volume, and more preferably consists essentially of an inorganic semiconductor.
  • Containing an inorganic perovskite-type material as a main component means that the inorganic perovskite-type material contains an amount capable of exhibiting the function of the present invention with respect to the entire volume of the second layer 105. Specifically, means that the content of the inorganic perovskite-type substance is more than 50% by volume with respect to the total volume of the second layer 105, for example. Preferably, it is 70% by volume or more.
  • the phrase “contains an organic or inorganic semiconductor (including a metal complex) as a main component” means that the aggregate or thin film (composite) containing the composite fine particles 10 is the function of the present invention with respect to the entire volume of the third layer 106.
  • the content of the organic or inorganic semiconductor is more than 50% by volume with respect to the total volume of the third layer 106 .
  • it is more than 90% by volume, and more preferably consists essentially of an organic or inorganic semiconductor (including a metal complex).
  • adjacent current paths may or may not be electrically connected to each other.
  • the "layer” in this embodiment means a film formed by one or more film formation processes, and is not limited to a flat one, and may not be integral. shall be
  • the materials and compositions of the three layers 104 to 106 are such that the energy level of the conduction band (LUMO, excited state) becomes higher in the order of the first layer 104, the second layer 105, and the third layer 106. It is determined.
  • the first layer 104 can have a valence band energy level of ⁇ 8 eV or more and a conduction band energy level of ⁇ 4 eV or less.
  • the second layer 105 can have a valence band energy level of ⁇ 6.0 eV or more and a conduction band energy level of ⁇ 3 eV or less.
  • the energy level of the conduction band of the third layer 106 is -2 eV or lower.
  • the first layer 104 is an aggregate of a plurality of inorganic semiconductor particles 20 formed on the negative electrode layer 102 and is a porous film having a plurality of voids between the inorganic semiconductor particles 20 .
  • the inorganic semiconductor particles 20 in contact with the second layer 105 contact the negative electrode layer 102 directly or indirectly through other inorganic semiconductor particles 20 so as to be electrically connected to the negative electrode layer 102. ing.
  • the contact area with the second layer 105 can be increased by having the first layer 104 which is a porous film.
  • the inorganic semiconductor contained in the inorganic semiconductor particles 20 preferably has an absorption wavelength in the ultraviolet region, such as titanium (IV) oxide and zinc oxide.
  • the inorganic semiconductor particles 20 are, for example, titanium (IV) oxide.
  • the photoelectric conversion element 100 is provided with an electron transport layer made of titanium (IV) oxide.
  • the thickness of the first layer 104 is preferably about 10 nm or more and 1000 nm or less, and more preferably about 50 nm or more and 500 nm or less. It should be noted that the first layer 104 may not be formed when applied to a solar cell.
  • the second layer 105 is a thin film that covers exposed portions of the surfaces of the inorganic semiconductor particles 20 in the manufacturing stage, that is, portions that are not in contact with the negative electrode layer 102 or the inorganic semiconductor particles 20 .
  • the second layer 105 does not need to cover the entire exposed portion, but preferably covers at least the positive electrode layer 101 side in order to form the current path.
  • the size and shape of the bandgap can be changed according to the number of ions selected from metal cations, halide anions, and organic cations.
  • the bandgap is narrowed and the material becomes responsive to long-wavelength light such as near-infrared light.
  • the halide anion is arranged at the apex of the regular octahedron centered on the metal ion, and the organic cation is arranged in the vicinity of the octahedral cube centered on the metal ion.
  • the structure is such that regular octahedra formed by metal ions and halogenated anions form a three-dimensional lattice, and organic cations enter the gaps between the lattices.
  • the third coating layer 4 of the composite fine particles 10 is an inorganic compound layer made of an inorganic perovskite-type substance
  • the composite fine particles 10 When forming the second layer 105 while being in contact with the inorganic perovskite-type substance constituting the second layer 105, the composite fine particles 10 The boundary between the inner third coating layer 4 and the inorganic perovskite material is substantially eliminated. Therefore, the light converted into visible light by the composite fine particles 10 is efficiently absorbed by the inorganic perovskite-type substance including the third coating layer 4 . Thereby, the conversion efficiency of light in the near-infrared region of the photoelectric conversion element 100 can be improved.
  • the composite fine particles 10 in the second layer 105 are 5 wt % or more with respect to the total mass of the second layer 105, because the sensitivity to light in the near-infrared region is improved. If the composite fine particles 10 in the second layer 105 exceed 30 wt %, it becomes difficult to form a perovskite-type substance, so 30 wt % or less is preferable.
  • the energy level of the valence band of the second layer 105 is preferably lower than the energy level of the valence band of the third layer 106 and is intermittently connected to the same energy level.
  • the composition of the second layer 105 (inorganic perovskite-type substance) satisfying these conditions include CH 3 NH 3 Pbl 3 , NH ⁇ CHNH 2 PbI 3 , CsPbI 3 and the like.
  • halide anions those having a different composition ratio of I and Cl or Br can also be used.
  • the third layer 106 is a thin film covering the surface (exposed surface) of the inorganic perovskite material contained in the second layer of the photoelectric conversion element precursor composed of the first layer 104 and the second layer 105. good.
  • the third layer 106 is formed of either a p-type organic semiconductor, an inorganic semiconductor, or an organometallic complex.
  • the thickness of the third layer 106 is preferably 1 nm or more and 100 nm or less, for example.
  • bathocuproine BCP
  • PDOT:PSS poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)
  • TPD N,N,N',N'-tetrakis(4-methoxyphenyl)-benzidine
  • Examples of the p-type inorganic semiconductor that constitutes the third layer 106 include CuI and CuSCN.
  • the photoelectric conversion element member of the present disclosure is formed by laminating a second layer 105 containing the composite fine particles 10 and a third layer 106 made of an aggregate or thin film mainly composed of an organic semiconductor or an inorganic semiconductor. .
  • a photoelectric conversion element provided with the photoelectric conversion element member of the present disclosure includes a hole transport layer and an electron transport layer, and the photoelectric conversion element member of the present disclosure is between the hole transport layer and the electron transport layer. may be placed.
  • FIGS. 4A to 4C show the energy band structure of each layer during operation of the photoelectric conversion element 100 according to this embodiment.
  • the energy level of the conduction band of the third layer 106 is higher than the Fermi level of the positive electrode layer 101 on the positive electrode layer 101 side, as shown in FIG. , the current from the positive electrode layer 101 to the negative electrode layer 102 is blocked.
  • the composite fine particles 10 forming the second layer 105 absorb the light and convert the wavelength into visible light.
  • An inorganic perovskite-type material absorbs the wavelength-converted light (FIG. 4(b)). Note that the dashed-line arrow and the solid-line arrow of the fine composite particles 10 in FIG. 4(b) indicate the same magnitude of energy.
  • the inorganic perovskite material By absorbing light, the inorganic perovskite material generates electrons e and holes h . It shifts to the band E v3 (the energy level of the valence band of the third layer 106) (FIG. 4(c)).
  • the first layer 104a is a porous film, but the photoelectric conversion element is not limited to this configuration.
  • FIG. 5 is a cross-sectional view of a modification of the photoelectric conversion element provided with the fine composite particles of FIG.
  • the photoelectric conversion element 100a includes a positive electrode layer (positive electrode member) 101, a negative electrode layer (negative electrode member) 102, and a photoelectric conversion layer 103a sandwiched therebetween.
  • the photoelectric conversion layer 103 a is composed of a layered second layer 105 and a layered third layer 106 .
  • the second layer 105 and the third layer 106 may be formed in a uniform film like the photoelectric conversion element 100a.
  • the photoelectric conversion element 100B is a photoelectric conversion element having a configuration suitable for use as an optical sensor.
  • FIG. 6 is a cross-sectional view of a photoelectric conversion element 100B having composite fine particles 10.
  • the photoelectric conversion element 100B mainly includes a positive electrode layer (positive electrode member) 101, a negative electrode layer (negative electrode member) 102, and a photoelectric conversion layer 103B sandwiched therebetween.
  • similar components are distinguished by attaching different letters after the same reference numerals. However, descriptions of the same components are omitted. Further, among the similar components, if the component has substantially the same functional configuration as the component that has been described, the description of that component will be omitted.
  • the photoelectric conversion layer 103B includes a first layer 104, a second layer 105 and a third layer 106B.
  • the photoelectric conversion layer 103 mainly has a first layer (electron transport layer) 104 composed of a plurality of particles 20 containing an inorganic semiconductor as a main component, and the surface of the first layer 104 a second layer 105 composed of an aggregate or thin film (composite) containing an inorganic perovskite-type substance as a main component and further containing the composite fine particles 10, and a plurality of particles or
  • a third layer 106B composed of the aggregate or thin film may be laminated.
  • containing an organometallic complex as a main component means that the content of the organometallic complex in the particles, aggregates thereof, or thin film is more than 50% by volume with respect to the total volume of the third layer. Say. Preferably, it is more than 90% by volume, and more preferably consists essentially of an inorganic semiconductor. That is, in the photoelectric conversion element 100, the positive electrode layer 101, the third layer 106B, the second layer 105, the first layer 104, and the negative electrode layer 102 are arranged in this order, and at least a current path from the positive electrode layer 101 to the negative electrode layer 102 is formed. It should be configured as follows.
  • the energy level of the conduction band (LUMO, excited state) is higher in the order of the first layer 104, the second layer 105, and the third layer 106B.
  • the energy level of the valence band (HOMO, ground state) of the bilayer 105 is determined to be higher than the energy level of the valence band of the third layer 106B.
  • the energy level of the second layer 105 is higher than the energy level of the first layer 104 and the energy level of the third layer 106B is higher than the energy level of the second layer 105 .
  • the first layer 104 can have a valence band energy level of ⁇ 8 eV or more and a conduction band energy level of ⁇ 4 eV or less.
  • the second layer 105 can have a valence band energy level of ⁇ 6.0 eV or more and a conduction band energy level of ⁇ 3 eV or less.
  • the energy level of the conduction band of the third layer 106 is -2 eV or less.
  • the third layer 106B is a thin film that covers the surfaces (exposed surfaces) of the inorganic perovskite-type substance molecules contained in the second layer 105 of the photoelectric conversion element precursor composed of the first layer 104 and the second layer 105.
  • should be Molecules of the organometallic complex forming the third layer 106B are obtained by coordinate bonding of an inorganic transition metal and an organic ligand.
  • 108A indicates the inorganic transition metal ions of the third layer 106B
  • 108B indicates the organic ligands of the third layer 106B.
  • the inorganic transition metal ions 108A are preferably localized in the form of a film on the second layer side so as to directly bond with the inorganic perovskite-type substance of the second layer 105 .
  • the organic ligand 108B is preferably localized in the form of a film on the side opposite to the second layer (positive electrode side).
  • the molecules of the organometallic complex 108B form the organic ligand 108B and the inorganic transition metal ion 108A in the current path from the positive electrode layer 101 side to the second layer 105 side.
  • the molecules of the inorganic perovskite-type substance so as to be arranged in order.
  • it is divided into a layer composed of inorganic transition metal ions and a layer composed of organic ligand ions.
  • the boundary between the two layers can be confirmed using, for example, a transmission electron microscope (TEM).
  • inorganic transition metal ions here include Eu 3+ , Cr 3+ and the like whose reduction level is LUMO, and Ru 2+ , Fe 2+ , Mn 2+ , Co 2+ and the like whose oxidation level is HOMO.
  • organic ligands herein include ligands of general metal complexes, such as (i) carboxyl group, nitro group, sulfo group, phosphate group, hydroxy group, oxo group, amino group, etc.
  • acetylacetonate-based organic ligand such as acetylacetone
  • acetylacetonate-based organic ligand means a number of transition metal ions via two oxygen atoms (e.g., It means an organic ligand capable of coordinative bonding while forming a six-membered ring).
  • the thickness of the third layer 106B is preferably, for example, about 1 nm or more and 10 nm or less. If the third layer 106B is thicker than 10 nm, the energy barrier becomes too thick to obtain a sufficient tunneling probability, thus hindering amplification of photocurrent in the photoelectric conversion layer 103B. If the thickness of the third layer 106B is less than 1 nm, the tunneling current will flow even when the light is not irradiated and the band is not bent, and the photodetection function of the photoelectric conversion layer 103B becomes meaningless.
  • FIGS. 7A to 7D show the energy band structure of each layer during operation of the photoelectric conversion element 100B according to this embodiment.
  • 108A indicates the inorganic transition metal ions of the third layer 106B
  • 108B indicates the organic ligands of the third layer 106B.
  • the energy level of the conduction band of the third layer 106B is higher than the Fermi level of the positive electrode layer 101 on the positive electrode layer 101 side, as shown in FIG. , the current from the positive electrode layer 101 to the negative electrode layer 102 is blocked.
  • the core (inorganic fine particles 1) of the composite fine particles 10 constituting the second layer 105 absorbs the light and converts the wavelength into visible light. do.
  • the inorganic perovskite material absorbs the wavelength-converted light to generate electrons e and holes h, the electrons e move to the conduction band Ec2 , and the holes h move to the valence band Ev2 (Fig. 7 ( b)).
  • the energy levels E v1 , E v2 , and E v3 of the valence bands of the first layer 104, the second layer 105, and the third layer 106B are E v2 >E v1 layer, and E v2 >E v3 . Therefore, as shown in FIG. 7(c), the number of holes generated in the second layer and transferred to the valence band is relatively high (low for holes) compared to the first and third layers. It is trapped in the valence band of the second layer, which becomes an energy state.
  • the potential energy of electrons is lowered and the energy level of the conduction band is lowered due to the influence (positive potential) of the holes that are trapped and concentrated and distributed. do. Since the energy level of the conduction band is greatly reduced closer to the second layer 105 where holes are trapped, the energy level of the conduction band of the third layer 106B is lower on the second layer side, and the positive electrode The layer side has a sharp shape. Therefore, the energy barrier of the third layer 106 becomes thin for electrons existing in the positive electrode layer 101, and tunneling to the negative electrode layer side becomes possible as shown in FIG. 7(d).
  • the photoelectric conversion element 100B of this modified example can realize a large amplification of the current directly generated by the irradiated light. Therefore, the photoelectric conversion element 100B of this modified example is suitable for use as an optical sensor.
  • the photoelectric conversion elements 100 and 100B of the present disclosure are mounted on a semiconductor substrate such as silicon or a glass substrate, for example, the following device configuration can be given.
  • a semiconductor substrate such as silicon or a glass substrate
  • the following device configuration can be given.
  • the method for producing composite fine particles 10 of the present disclosure includes an inorganic fine particle synthesis step, a first coating layer forming step, a second coating layer forming step, and a third coating layer forming step.
  • the inorganic fine particle synthesizing step the inorganic fine particles 1 are synthesized.
  • the method for synthesizing the inorganic fine particles 1 is not particularly limited, but examples thereof include a precipitation method and a hydrothermal synthesis method.
  • Ln (lanthanoid ) oxides such as Gd2O3 , Er2O3 , Tm2O3 , Ho2O3 , Yb2O3 , Y2O3 or Ln halides such as , ErCl 3 , ErF 3 , TmCl 3 , TmF 3 , HoCl 3 , HoF 3 and the like are used to synthesize trifluoroacetic acid salts or acetylacetonate salts.
  • first coating layer forming step In the first coating layer forming step, the first coating layer 2 is formed on the inorganic fine particles 1 obtained in the inorganic fine particle synthesizing step.
  • a method for forming the first coating layer 2 is not particularly limited. Examples include a precipitation method and a hydrothermal synthesis method. Specifically, lanthanoid oxides Gd 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Ho 2 O 3 , Yb 2 O 3 and Nd 2 O 3 are used to synthesize trifluoroacetate. Further, inorganic fine particles 1 and sodium trifluoroacetate are added thereto, and reacted under nitrogen or argon atmosphere at high temperature (100 to 400° C.). The solution after the reaction is cooled, an organic solvent such as ethanol is added as necessary, and then centrifuged to obtain inorganic fine particles 1 coated with the first coating layer 2 (first coated particles). The formation of the first coating layer may be performed multiple times.
  • the second coating layer 3 is formed on the surface of the first coated particles.
  • a method for forming the second coating layer 3 is not particularly limited. Specifically, for example, NaBF 4 dimethylformamide solution is dropped into a solvent in which the first coated particles are dispersed, stirred at room temperature (20 to 30° C.) under a nitrogen atmosphere for 30 to 120 minutes, and centrifuged. A powder is obtained by separation.
  • the obtained powder is dispersed in a solvent, a multidentate organic ligand (e.g., indocyanine dye) to which a transition metal ion (e.g., Y 3+ or Pb 2+ ) is bonded is added, and the mixture is subjected to ultrasonication at room temperature for 10 minutes or more. Stir in. By separating by centrifugation after adding an organic solvent such as ethanol as necessary, the first coated particles (second coated particles) coated with the second coating layer are obtained.
  • a multidentate organic ligand e.g., indocyanine dye
  • a transition metal ion e.g., Y 3+ or Pb 2+
  • the third coating layer 4 is formed on the surfaces of the second coated particles.
  • a method for forming the third coating layer 4 is not particularly limited. Methods for forming the third coating layer 4 include, for example, a precipitation method and a hydrothermal synthesis method. Specifically, for example, the second coated particles are reacted with a solution containing cesium oleate synthesized from cesium carbonate and lead halide (PbX 2 ). The temperature is 120 to 200° C. under a nitrogen atmosphere. After the reaction, the solution is cooled and centrifuged to separate fine particles. Composite fine particles 10 are obtained by firing the separated fine particles (for example, at 100° C. to 200° C.).
  • FIG. 8A to 8E are cross-sectional views of an object to be processed in the manufacturing process of the photoelectric conversion element 100.
  • FIG. The photoelectric conversion element 100 can be manufactured mainly through the following procedures.
  • a base material provided with a negative electrode layer 102 for forming a photoelectric conversion layer 103 is prepared.
  • an electrode member that functions as a negative electrode layer and has transparent conductivity is used.
  • the buffer layer 107 may not be formed.
  • the buffer layer 107 functions as an electron transport layer or a hole blocking layer.
  • the buffer layer 107 can be formed by applying a material solution to the negative electrode layer 102 using a spin coating method or the like and heating (drying) it. This heating may be performed, for example, at about 120 to 450° C. for about 10 to 60 minutes. It is preferable to adjust the material application conditions (application time, etc.) so that the thickness of the buffer layer 107 is, for example, about 1 to 100 nm.
  • the first layer 104 can also be formed by applying a solution of the material and heating. This heating may also be performed, for example, at about 120 to 450° C. for about 10 to 60 minutes. It is preferable to adjust the material application conditions (application time, etc.) so that the thickness of the first layer 104 is, for example, about 10 to 1000 nm, preferably about 50 to 500 nm.
  • a spin coating method, a dipping method, or the like is used to coat the raw material of the inorganic perovskite-type substance, which is the main component, and the composite fine particles 10 on the surfaces of the inorganic semiconductor particles 20.
  • the second layer 105 may be formed by applying the containing solution and heating it. This heating may be performed, for example, at about 40 to 100° C. for about 5 to 10 minutes. The thickness of the second layer 105 is adjusted by the material application conditions (application time, etc.).
  • a third layer 106 may be formed on the second layer 105.
  • a material containing a p-type organic semiconductor or an inorganic semiconductor as a main component is deposited on the second layer 105 using a spin coating method, a dip method, or the like, or a solution of the material is applied.
  • a trilayer 106 may be formed.
  • the third layer 106 is formed in a film shape mainly on the exposed portion of the surface of the second layer 105 on the positive electrode layer 101 side (the side opposite to the negative electrode layer 102 ).
  • the application and heating of the solution are preferably performed in two steps. That is, in the first step, a solution of an inorganic transition metal such as europium is applied and heated, and in a second step, a solution of an organic ligand such as terpyridine is applied and heated.
  • the third layer 106B consists of the layer 108A made of an inorganic transition metal and the layer 108B made of an organic ligand in order from the second layer 105 side. , is laminated.
  • an electrode member (positive electrode layer) 101 that functions as a positive electrode and has conductivity is formed on the third layer 106, thereby obtaining the photoelectric conversion element 100 of the present embodiment. can be obtained.
  • the multidentate organic ligands of the second coating layer 3 absorb the long-wavelength light in the near-infrared or infrared region with high efficiency, and convert it into visible light/ultraviolet light. It is configured such that it is converted into short-wavelength light such as light, and the converted light is reabsorbed by the inorganic perovskite material of the second layer 105 and converted into electric power. Therefore, according to the fine composite particles 10 of the present embodiment, it becomes possible to generate photoelectric conversion or electromotive force from long-wavelength light, which has been difficult in the past.
  • the composite fine particles 10 of the present embodiment can suppress the thermal vibration of the multidentate organic ligands and perform energy transfer reliably and efficiently. As a result, energy loss can be reduced. Therefore, even if the light absorbed by the polydentate organic ligand is weak, excellent photosensitizing properties can be realized.
  • the resulting mixture was cooled to room temperature while still under N 2 atmosphere, ethanol was added thereto, and then centrifuged to obtain first intermediate particles (Gd 2 O 2 S doped with Er and Yb: Er (5%), Yb (20%), particle size 10-20 nm).
  • the particle size of the first intermediate particles was obtained from the observed image (FIG. 9(a)) obtained by SEM observation.
  • second intermediate particles (first intermediate particles coated with NaYbF4 , particle size of 25 nm or less) were obtained by centrifugally recovering the powder from the resulting mixture.
  • the particle size of the second intermediate particles was obtained from the observed image (FIG. 9(b)) obtained by SEM observation.
  • fourth intermediate particles third intermediate particles coated with ICG-Y, particle size of 40 nm or less, nanoparticles B
  • the particle size of the fourth intermediate particles was obtained from the observed image (FIG. 9(d)) obtained by SEM observation.
  • Nanoparticles A (comparative particles without second coating layer) and production thereof)
  • a mixture was obtained by adding 130 g of Y 2 O 3 to 10 mL of 50% aqueous trifluoroacetic acid. The resulting mixture was stirred at 80° C. under reduced pressure for 30 minutes. 272 g of sodium trifluoroacetate and 170 mg of the third intermediate particles obtained above were then added to the mixture. The resulting mixture was then stirred at 150° C. for 180 minutes under nitrogen. Next, the powder was recovered from the resulting mixture by centrifugal separation to obtain nanoparticles A (comparative fine particles in which the second coating layer was not present).
  • a member substantially made of antimony-doped tin oxide (ATO) was prepared as a member that was provided on the base material and became the negative electrode layer.
  • ATO antimony-doped tin oxide
  • One surface of this member was spin-coated with 200 ⁇ l of a 0.18 M ethanol solution of titanium diisopropylato diacetylacetonate at a rotation speed of 3000 rpm.
  • the mixed solution spin-coated on the member was heated at 500° C. for 30 minutes to form a buffer layer substantially composed of a titanium oxide (TiO 2 ) dense film.
  • a mixed solution containing a titanium oxide (TiO 2 ) paste (PST18NR, manufactured by Nikki Shokubai Kasei Co., Ltd.) and ethanol at a weight ratio of 1:3.5 is applied to the buffer layer formed as described above. 120 ⁇ l was spin-coated at 6000 rpm. Subsequently, the mixed solution spin-coated on the buffer layer was heated at 120° C. for 10 minutes and then heated at 450° C. for 1 hour in order to obtain a plurality of particles substantially made of titanium oxide. A first layer (porous membrane) was formed.
  • a positive electrode layer (Au) is formed (evaporated) on the side opposite to the negative electrode layer with the laminate consisting of the first layer, the second layer, and the third layer sandwiched therebetween, and in contact with the third layer.
  • a photoelectric conversion element was manufactured by the following.
  • the current-voltage characteristics of the photoelectric conversion element manufactured in 5 above were measured.
  • the wavelength of the irradiated light was 750 nm or more, and the irradiance was 1 sun.
  • FIG. 11 is a graph showing changes in absorptance of excitation light.
  • the horizontal axis of FIG. 11 indicates the wavelength (nm), and the vertical axis of FIG. 11 indicates the intensity (Counts/s).
  • the solid line in FIG. 11 indicates the intensity of the original excitation light, and the dotted line in FIG. 11 indicates the intensity after irradiating the composite fine particles A obtained in 2 above with the excitation light. From the results of FIG. 11, it was confirmed that the composite fine particles A obtained in 2 above efficiently absorbed light of 700 nm or longer.
  • the dashed line in FIG. 11 indicates the result of nanoparticle A produced in the same manner as composite fine particle A except that the second coating layer (infrared absorbing dye) was not formed. It was confirmed that light with a wavelength of 700 nm or more is hardly absorbed without the second coating layer.
  • the same results as above were obtained with composite fine particles B obtained in 3 above.
  • FIG. 12 is a graph showing the spectrum of the wavelength-converted light obtained by irradiating the composite fine particles A obtained in 2 above with the excitation light shown in FIG.
  • the horizontal axis of FIG. 12 indicates the wavelength (nm), and the vertical axis of FIG. 12 indicates the intensity (Counts/s). It shows peaks at three wavelengths (around 530 nm, around 550 nm, and around 680 nm). From the results of FIGS. 11 and 12, it was found that the irradiated light with a wavelength of 700 nm or longer was converted into these three lights.
  • the internal luminescence quantum yield (visible light region) of the composite fine particles A obtained in 2 above was 5.98% when excited by near-infrared light.
  • FIG. 13 is a graph showing the spectrum of the wavelength-converted light obtained by irradiating the composite fine particles B obtained in 3 above with the excitation light shown in FIG.
  • the horizontal axis of FIG. 13 indicates the wavelength (nm), and the vertical axis of FIG. 13 indicates the intensity (Counts/s). It shows peaks at four wavelengths (around 405 nm, around 520 nm, around 550 nm, and around 680 nm). From the results of FIGS. 11 and 13, it was found that the irradiated light with a wavelength of 700 nm or more was converted into these three lights.
  • the internal emission quantum yield (visible light region) of the composite fine particles B obtained in 3 above was 6.12% when excited by near-infrared light.
  • the dotted line in FIG. 13 is the result for the fourth intermediate particles (third intermediate particles coated with ICG-Y, nanoparticles B) without the third coating layer.
  • the emission intensity around 405 nm, around 520 nm, and around 550 nm decreased, and the internal emission quantum yield (visible light region) was 2.5 nm. was 54%. It is presumed that this is because the nanoparticles B do not have the third coating layer, and thus energy deactivation is likely to occur. Since the nanoparticle B does not have the third coating layer, the emission intensity (efficiency) is reduced and the upconversion intensity is reduced (upconversion is less likely to occur, and only emission on the long wavelength side is observed).
  • FIG. 14 is a diagram showing current-voltage characteristics of the photoelectric conversion element manufactured in 5 above.
  • the horizontal axis of FIG. 14 is voltage (V), and the vertical axis is current density (mA/cm 2 ).
  • V voltage
  • mA/cm 2 current density
  • FIG. 14 it was found that the photoelectric conversion element produced in 5 above generated power when irradiated with light having a wavelength of 750 nm or longer. It is considered that this is because the inorganic perovskite-type substance absorbed the light that was efficiently wavelength-converted by the composite fine particles B obtained in 3 above.
  • the fill factor ff obtained from the open-circuit voltage of 1.06 V and the short-circuit current of 2.47 mA/cm 2 of the photoelectric conversion element manufactured in 5 above was 0.45. From the above, it was found that by using the fine composite particles and the photoelectric conversion device of the present invention, excellent detection sensitivity to light in the near-infrared or infrared region can be obtained

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170358757A1 (en) * 2014-11-06 2017-12-14 Postech Academy-Industry Foundation Perovskite nanocrystalline particles and optoelectronic device using same
JP2018168056A (ja) 2017-03-29 2018-11-01 美貴 長谷川 コア／シェル型Ｌｎ錯体ナノ粒子
JP2019135272A (ja) * 2016-06-07 2019-08-15 コニカミノルタ株式会社 サーモクロミック性二酸化バナジウム含有粒子及びその製造方法と、サーモクロミックフィルム及びその製造方法
JP2021147994A (ja) 2020-03-16 2021-09-27 日立建機株式会社 作業機械

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170358757A1 (en) * 2014-11-06 2017-12-14 Postech Academy-Industry Foundation Perovskite nanocrystalline particles and optoelectronic device using same
JP2019135272A (ja) * 2016-06-07 2019-08-15 コニカミノルタ株式会社 サーモクロミック性二酸化バナジウム含有粒子及びその製造方法と、サーモクロミックフィルム及びその製造方法
JP2018168056A (ja) 2017-03-29 2018-11-01 美貴 長谷川 コア／シェル型Ｌｎ錯体ナノ粒子
JP2021147994A (ja) 2020-03-16 2021-09-27 日立建機株式会社 作業機械

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LI MING; YUAN XIAOQIN; RUAN HAORAN; WANG XIANDONG; LIU YONGPING; LU ZHENHUAN; HAI JIEFENG: "Synthesis of PbS-CH3NH3PbI3core-shell nanoparticles with enhanced photoelectric properties", JOURNAL OF ALLOYS AND COMPOUNDS, ELSEVIER SEQUOIA, LAUSANNE., CH, vol. 706, 24 February 2017 (2017-02-24), CH , pages 395 - 400, XP029950258, ISSN: 0925-8388, DOI: 10.1016/j.jallcom.2017.02.236 *

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